CN111655478A

CN111655478A - Fiberglass composite covers for foldable electronic displays and methods of making the same

Info

Publication number: CN111655478A
Application number: CN201980010295.1A
Authority: CN
Inventors: 侯军; 郭冠廷; K·R·姆卡蒂; R·L·史密斯三世
Original assignee: Corning Inc
Current assignee: Corning Inc
Priority date: 2018-01-25
Filing date: 2019-01-25
Publication date: 2020-09-11
Also published as: EP3743274A1; WO2019147915A1; US20200371273A1; US11709291B2; TW201935039A

Abstract

An optically clear fiber glass cover substrate for an electronic display. The cover substrate includes an optically clear fiber glass composite layer comprising a fiber glass layer embedded in a matrix material and an optically clear hard coat layer bonded to a top surface of the optically clear fiber glass composite layer. The bottom surface of the optically transparent fiberglass composite layer may define a bottommost outer surface of the cover substrate. The bottommost outer surface of the cover substrate may be disposed over a display surface of the electronic display, thereby protecting the display surface from damage.

Description

Fiberglass composite covers for foldable electronic displays and methods of making the same

Background

Cross Reference to Related Applications

This application claims priority from U.S. provisional application serial No. 62/621686 filed 2018, 1, 25, 35u.s.c. § 119, which is hereby incorporated herein by reference in its entirety.

Technical Field

The present disclosure relates to a fiberglass composite overlay substrate. In particular, the present disclosure relates to an optically transparent fiber glass cover substrate for a display.

Background

Cover substrates for displays of electronic devices protect the display screen and provide an optically transparent surface through which a user can view the display screen. In recent years, the development of electronic devices (e.g., handheld and wearable devices) has tended towards lighter devices with improved reliability. The different components of these devices, including protective components such as cover substrates, are reduced in weight to produce lighter devices.

In addition, flexible cover substrates have been developed to accommodate flexible and foldable display panels. However, when the flexibility of the cover substrate is increased, other characteristics of the cover substrate may be sacrificed. For example, in some cases, increasing flexibility may increase weight, decrease optical clarity, decrease scratch resistance, decrease puncture resistance, and/or decrease thermal durability, all of which can result in visible damage to the cover substrate and/or failure of the display and/or device.

Plastic films have good flexibility but suffer from poor mechanical durability. Polymer films with hard coatings exhibit improved mechanical durability, but often result in higher manufacturing costs and reduced deflection. Thin monolithic glass solutions have excellent scratch resistance but are challenging to meet both deflection and puncture resistance specifications. Ultra-thin glass can have good bend radii, but can suffer from reduced puncture resistance problems.

Accordingly, there is a continuing need for cover substrates for consumer products (e.g., cover substrates for protecting display screens). And in particular, to cover substrates for consumer devices that include flexible components such as flexible displays.

Disclosure of Invention

The present disclosure relates to a cover substrate, such as a flexible cover substrate for protecting flexible or sharp bend components (e.g., display components). These cover substrates include fiberglass composite layers and hard coatings that do not adversely affect the flexibility or curvature of the assembly while also protecting the assembly from mechanical forces. The flexible cover substrate may include a flexible optically clear fiber glass composite layer and an optically clear hard coating.

Some embodiments relate to a cover substrate for an electronic display, the cover substrate comprising: an optically clear fiberglass composite layer comprising a fiberglass layer embedded in a matrix material and a bottom surface defining a bottommost outer surface overlying a substrate, and an optically clear hard coat layer bonded to a top surface of the optically clear fiberglass composite layer.

Some embodiments relate to an article comprising a cover substrate comprising: an optically clear fiber glass composite layer including a bottom surface defining a bottommost surface overlying a substrate and an optically clear hard coat layer bonded to a top surface of the optically clear fiber glass composite layer

In some embodiments, an article according to the preceding paragraph may be a consumer electronic product comprising: a housing comprising a front surface, a back surface, and side surfaces; an electronic assembly at least partially within the housing, the electronic assembly including a controller, a memory, and a display, the display being located at or adjacent to the front surface of the housing; and a cover substrate disposed over the display or forming at least a portion of the housing.

In some embodiments, a cover substrate according to an embodiment of any of the preceding paragraphs may include an optically clear adhesive layer disposed on the optically clear fiber glass composite layer and bonding the optically clear hardcoat layer to the optically clear fiber glass composite layer. In some embodiments, the optically clear adhesive layer comprises a thickness of 5 micrometers (μm, microns) to 50 microns.

In some embodiments, the fiber glass layer of the optically transparent fiber glass composite layer according to embodiments of any of the preceding paragraphs may comprise a glass material having a first refractive index, and the matrix material of the optically transparent fiber glass composite layer may have a second refractive index, and the difference between the first refractive index and the second refractive index is 0.05 or less.

In some embodiments, the fiberglass layer of the optically transparent fiberglass composite layer according to an embodiment of any preceding paragraph may be a woven (woven) fiberglass layer.

In some embodiments, the matrix material of the optically transparent fiber glass composite layer according to embodiments of any of the preceding paragraphs may comprise a crosslinked polymeric material.

In some embodiments, an optically transparent fiber glass composite layer according to an embodiment of any of the preceding paragraphs may have a thickness of 25 microns to 200 microns.

In some embodiments, the fiberglass layer of the optically transparent fiberglass composite layer according to an embodiment of any of the preceding paragraphs may have a thickness of from 10 microns to 100 microns.

In some embodiments, an optically clear hard coat according to an embodiment of any preceding paragraph can have a pencil hardness of 8H or greater.

In some embodiments, the optically clear hard coat according to an embodiment of any of the preceding paragraphs may be a polymer layer.

In some embodiments, a cover substrate according to embodiments of any of the preceding paragraphs may have a bend radius of 3mm or less.

In some embodiments, the topmost exterior surface of the cover substrate according to embodiments of any preceding paragraph may include a substantially planar central region and a curved perimeter region disposed about all or part of the substantially planar central region.

In some embodiments, an optically transparent fiber glass composite layer according to an embodiment of any of the preceding paragraphs may have an elastic modulus of 200MPa to 2500 MPa.

In some embodiments, the optically transparent fiber glass composite layer according to an embodiment of any preceding paragraph has a first refractive index, and the optically transparent hard coat layer according to an embodiment of any preceding paragraph has a second refractive index, and the difference between the first refractive index and the second refractive index is 0.05 or less.

In some embodiments, a cover substrate according to embodiments of any of the preceding paragraphs may have an impact resistance defined by the ability of the cover substrate to avoid failure at a minimum pen drop height in a pen drop test, which is 7 centimeters.

Some embodiments relate to an electronic display assembly comprising an electronic display comprising a display surface and a cover substrate disposed over the display surface, the cover substrate comprising an optically clear fiber glass composite layer disposed over the display surface and an optically clear hardcoat layer bonded to a top surface of the optically clear fiber glass composite layer.

In some embodiments, an electronic display according to an embodiment of any of the preceding paragraphs may be a flexible electronic display.

In some embodiments, the cover substrate according to embodiments of any of the preceding paragraphs is configured to protect the flexible electronic display from impact forces, and the cover substrate has an impact resistance defined by the ability of the cover substrate to avoid failure at a minimum pen drop height of 7 centimeters in a pen drop test.

In some embodiments, an electronic display assembly according to an embodiment of any of the preceding 3 paragraphs may comprise an optically clear adhesive layer disposed on a display surface of the electronic display and bonding the optically clear fiberglass composite layer to the display surface.

In some embodiments, an electronic display assembly according to embodiments of any of the preceding 4 paragraphs may be free of a glass layer disposed between the display surface and the optically clear fiberglass composite layer.

Some embodiments relate to a method of manufacturing a cover substrate for an electronic display, the method comprising forming an optically clear fiberglass composite layer (which includes a fiberglass layer embedded in a matrix material and a bottom surface defining a bottommost outer surface of the cover) and an optically clear hard coat layer bonded to a top surface of the optically clear fiberglass composite layer.

In some embodiments, a method according to an embodiment of any of the preceding paragraphs may comprise bonding an optically clear hardcoat layer to a top surface of an optically clear composite layer with an optically clear adhesive layer. In some embodiments, a method according to an embodiment of any preceding paragraph may comprise: forming an optically clear hardcoat layer on a top surface of the optically clear fiber glass composite layer, and forming the optically clear hardcoat layer on the top surface such that the optically clear hardcoat layer is bonded to the top surface.

Drawings

The accompanying drawings, which are incorporated in and form a part of the specification, illustrate embodiments of the present disclosure. The drawings serve to further explain the principles of the disclosed embodiments and to enable a person skilled in the pertinent art to make and use the same in conjunction with the description. The drawings are intended to be illustrative, not restrictive. While the disclosure is described in the context of these embodiments, it will be understood that it is not intended to limit the scope of the disclosure to these particular embodiments. In the drawings, like reference numbers indicate identical or functionally similar elements.

Fig. 1 shows a cover substrate according to some embodiments.

Fig. 2 shows a cover substrate according to some embodiments.

FIG. 3 shows an optically transparent fiberglass composite layer according to some embodiments.

Fig. 4 shows a cross-sectional view of the cover substrate of fig. 1 after the substrate is bent.

Fig. 5 shows an electronic display assembly according to some embodiments.

Fig. 6A shows a first test sample configuration. Fig. 6B shows a second test sample configuration. Fig. 6C shows a third test sample configuration.

Fig. 7A is a photograph of a broken electronic display. Fig. 7B is a first microscope image of a broken electronic display. Fig. 7C is a second microscope image of a broken electronic display.

Fig. 8A-8C show a cover substrate according to various embodiments.

Fig. 9 shows a cover substrate comprising a coating according to some embodiments.

Fig. 10 shows a consumer product according to some embodiments.

Detailed Description

The following examples of the present disclosure are illustrative, and not restrictive. Other suitable modifications and adjustments will generally be apparent to those skilled in the art based on various conditions and parameters, which are within the spirit and scope of this disclosure.

Cover substrates for consumer products can function to reduce undesirable reflections, prevent the formation of mechanical defects (e.g., scratches or cracks) in the cover substrate, and/or provide an easily cleaned transparent surface, among other things. The cover substrates disclosed herein may be integrated into another article, such as an article (or display article) having a display screen (e.g., consumer electronics including mobile phones, tablets, computers, navigation systems, and wearable devices (e.g., watches), etc.), a construction article, a transportation article (e.g., vehicles, trains, aircraft, nautical devices, etc.), an electrical article, or any article that may benefit from partial transparency, scratch resistance, abrasion resistance, or a combination thereof. An exemplary article incorporating any of the cover substrates disclosed herein is a consumer electronic device comprising: a housing having a front surface, a back surface, and side surfaces; an electronic assembly located at least partially within or entirely within the housing and including at least a controller, a memory, and a display located at or adjacent to a front surface of the housing; and a cover substrate positioned at or above the front surface of the housing so as to be positioned above the display. The cover substrate may include any of the cover substrates disclosed herein. In some embodiments, at least one of the housing or a portion of the cover substrate comprises a cover substrate as disclosed herein.

The cover substrate also serves to protect sensitive components of the consumer product from mechanical damage (e.g., punctures and impact forces). For consumer products that include flexible, foldable, and/or sharp curved portions (e.g., flexible, foldable, and/or sharp curved display screens), a cover substrate for protecting a display screen should protect the screen while also preserving the flexibility, foldability, and/or curvature of the screen. In addition, the cover substrate should be resistant to mechanical damage (e.g., scratches and chipping) so that the user can enjoy the display screen in a glance.

Thick monolithic glass substrates may provide sufficient mechanical properties, but these substrates can be bulky and cannot be folded to tighter radii for use in foldable, flexible, or sharp curved consumer products. While highly flexible cover substrates (e.g., plastic substrates) may not provide sufficient puncture resistance, scratch resistance, and/or shatter resistance desired for consumer products.

The cover substrates disclosed herein include a composite fiberglass layer and a polymeric top layer (e.g., a hardcoat or scratch resistant layer) bonded to the composite fiberglass layer. In some embodiments, a polymer top layer may be laminated to a composite fiberglass layer. The composite fiberglass layer may include a fiberglass layer and an index-matching polymer matrix. The index matching between the fiber glass layer material and the matrix material may provide the desired optical transparency for the composite fiber glass layer.

The combination of a composite fiberglass layer for covering a substrate with a polymeric topcoat as discussed herein may provide the mechanical properties needed to prevent scratching, puncture and/or impact damage while providing the flexibility possessed by polymeric materials. And the mechanical properties (e.g., stiffness) of the cover substrates discussed herein can be adjusted by, for example, changing the modulus of the matrix material of the composite fiberglass layer and/or the fiberglass density. Such adjustability may facilitate convenient customization of cover substrates for different types of consumer products (e.g., different flexible and/or wearable electronic devices).

The cover substrate discussed herein provides a flexible and damage resistant cover for a flexible electronic device by employing a layer that combines the strength of a glass material and the flexibility of a plastic material. This results in a flexible cover substrate having improved puncture resistance and/or impact resistance compared to cover substrates comprising a glass layer (e.g., an ultra-thin glass layer) and cover substrates formed only from plastic films and/or plastic layers. And these beneficial properties can be combined while maintaining the ability to bend to a small bend radius (e.g., about 3 millimeters (mm), 2mm, or 1 mm). The network of fiberglass embedded in the matrix material provides cushioning for puncture impacts by absorbing impact forces and spreading them over a large area. And the polymeric top layer may provide scratch resistance as well as additional impact and/or puncture resistance. In some embodiments, the polymeric top layer can be a polymeric hard coat layer having a pencil hardness of 8H or greater, such as 9H or greater. Pencil hardness was measured according to ASTM D3363. The combination of the composite fiberglass layer and the polymeric top layer discussed herein can reduce the size of fractures formed by the cover substrate during use as compared to cover substrates comprising ultra-thin glass (i.e., glass having a thickness of 75 microns or less).

In some embodiments, the cover substrate may include only a composite fiberglass layer bonded to a polymer top layer for the purpose of providing the desired mechanical properties. In such embodiments, such a structure may reduce the number of layers to thereby produce a flexible cover substrate that is capable of adequately protecting sensitive components of consumer products from mechanical damage during use. By reducing the number of layers to an amount sufficient to protect sensitive components of the consumer product, stress buildup between layers of the cover substrate that may cause the cover substrate to fail may be reduced. Furthermore, reducing the number of layers eliminates any inflexibility added by the extra layers. By building the required mechanical properties into both layers, the cover substrate can be manufactured at low cost and with low failure probability.

Fig. 1 shows a cover substrate 100 according to some embodiments. The cover substrate 100 includes: an optically clear fiber glass composite layer 110 and an optically clear hardcoat layer 120 bonded to the optically clear fiber glass composite layer 110. In some embodiments, the optically clear hard coat layer 120 may be bonded to the top surface 114 of the optically clear fiber glass composite layer 110. In some embodiments, an optically clear hard coat layer 120 may be disposed on the top surface 114 of the optically clear fiber glass composite layer 110.

As used herein, "disposed on … …" means that the first layer is in direct contact with the second layer. A first layer "disposed on" a second layer may be deposited onto, formed on, placed on, or in any other way applied directly to the second layer. In other words, if the first layer is disposed on the second layer, no other layer is disposed between the first layer and the second layer. The description of a first layer as "bonded to" a second layer refers to the direct bonding of the layers to each other, either by direct contact and/or bonding between the two layers or via an adhesive layer. For example, in some embodiments, optically clear hardcoat layer 120 can be bonded to top surface 114 of optically clear fiber glass composite layer 110 via an optically clear adhesive (see, e.g., optically clear adhesive layer 130 in fig. 2). For another example, the optically clear hardcoat layer 120 may be bonded to the top surface 114 of the optically clear fiber glass composite layer 110 by forming or depositing the optically clear hardcoat layer 120 on the optically clear fiber glass composite layer 110. If a first layer is described as being "disposed over" a second layer, there may or may not be other layers between the first and second layers.

As used herein, "optically transparent" means that the average transmission through a 1.0mm thick sheet of material is 70% or greater over the wavelength range of 400nm to 700 nm. In some embodiments, the optically transparent material can have an average transmission of 75% or greater, 80% or greater, 85% or greater, or 90% or greater over a wavelength range of 400 nanometers (nm) to 700nm for a sheet of material that is 1.0mm thick therethrough. The average transmittance in the wavelength range of 400nm to 700nm is calculated by measuring the transmittance at all wavelengths from 400nm to 700nm and averaging the measurements.

In some embodiments, the bottom surface 112 of the optically transparent fiber glass composite layer 110 may define the bottommost outer surface of the cover substrate 100. In such embodiments, the bottom surface 112 of the optically transparent fiberglass composite layer 110 may be disposed above a display surface of an electronic display in use (e.g., display surface 514 as shown in fig. 5). In some embodiments, the top surface 124 of the optically clear hardcoat layer 120 may define the topmost, exterior user-facing surface of the cover substrate 100. As used herein, the terms "top surface" or "topmost surface" and "bottom surface" or "bottommost surface" relating to the top and bottom surfaces of a layer or article will be oriented as it would be the case in normal use of the device, and are intended to use the top surface as the user-facing surface. For example, when incorporated into a handheld consumer electronic product having an electronic display, the "top surface" of the cover substrate refers to the top surface of the cover substrate that the cover substrate is held by a user while the electronic display is viewed through the cover substrate.

In some embodiments, the optically transparent fiber glass composite layer 110 may have a thickness 116, measured from the bottom surface 112 to the top surface 114 of the optically transparent fiber glass composite layer 110, of 25 micrometers (microns) to 200 microns, including any and all subranges therebetween. For example, the thickness 116 may be: 25 microns, 30 microns, 35 microns, 40 microns, 45 microns, 50 microns, 60 microns, 70 microns, 75 microns, 80 microns, 90 microns, 100 microns, 110 microns, 120 microns, 125 microns, 130 microns, 140 microns, 150 microns, 160 microns, 170 microns, 175 microns, 180 microns, 190 microns, 200 microns, or in a range where any two of these values are endpoints. For example, the thickness 116 may be: 25 to 190 microns, or 25 to 180 microns, or 25 to 170 microns, or 25 to 160 microns, or 25 to 150 microns, or 25 to 140 microns, or 25 to 130 microns, or 25 to 120 microns, or 25 to 110 microns, or 25 to 100 microns, or 25 to 90 microns, or 25 to 80 microns, or 25 to 70 microns, or 25 to 60 microns, or 25 to 50 microns, or 25 to 40 microns.

In some embodiments, the optically transparent fiber glass composite layer 110 may have a modulus of elasticity of 200MPa (megapascals) or greater measured in the first transverse direction 190 and/or the second transverse direction 192 parallel to the top surface 114 of the optically transparent fiber glass composite layer 110. In some embodiments, the optically transparent fiber glass composite layer 110 may have an elastic modulus in the first transverse direction 190 and/or the second transverse direction 192 of 200MPa to 2500MPa, including any and all subranges therebetween. For example, the optically transparent fiberglass composite layer 110 may have an elastic modulus in the first transverse direction 190 and/or the second transverse direction 192 of: 200MPa, 250MPa, 300MPa, 400MPa, 500MPa, 600MPa, 700MPa, 750MPa, 800MPa, 900MPa, 1000MPa, 1100MPa, 1200MPa, 1300MPa, 1400MPa, 1500MPa, 1600MPa, 1700MPa, 1800MPa, 1900MPa, 2000MPa, 2100MPa, 2200MPa, 2300MPa, 2400MPa, 2500MPa, or within a range in which any two of these values are endpoints. For example, the optically transparent fiberglass composite layer 110 may have an elastic modulus in the first transverse direction 190 and/or the second transverse direction 192 of: 200 to 2400MPa, or 200 to 2300MPa, or 200 to 2200MPa, or 200 to 2100MPa, or 200 to 2000MPa, or 200 to 1900MPa, or 200 to 1800MPa, or 200 to 1700MPa, or 200 to 1600MPa, or 200 to 1500MPa, or 200 to 1400MPa, or 200 to 1300MPa, or 200 to 1200MPa, or 200 to 1100MPa, or 200 to 1000MPa, or 200 to 900MPa, or 200 to 800MPa, or 200 to 700MPa, or 200 to 600MPa, or 200 to 500MPa, or 200 to 400 MPa. A lower modulus of elasticity (e.g., 200MPa to 2500MPa) in the first transverse direction 190 and/or the second transverse direction 192 can minimize the force that can cause the cover substrate to bend, for example, during use or manufacturing. In addition, the lower modulus of elasticity may minimize internal stresses within the cover substrate. Internal stresses within the cover substrate can cause failure of the cover substrate during use and/or can transfer to and damage the attached display device.

In some embodiments, the optically transparent fiber glass composite layer 110 may have an elastic modulus in the first transverse direction 190 and/or the second transverse direction 192 of greater than 2500 MPa. The orientation of the fibers in the optically transparent fiberglass composite layer 110 may be adjusted to produce a desired modulus of elasticity in the first transverse direction 190 and/or the second transverse direction 192. In some embodiments, the modulus of elasticity in the first transverse direction 190 and the second transverse direction 192 may be the same. In some embodiments, the modulus of elasticity in the first and second

transverse directions

190 and 192 may be different (i.e., one may be less than or greater than the other).

The optically transparent hard coating 120 may comprise an optically transparent material having a pencil hardness greater than the pencil hardness of the optically transparent fiber glass composite layer 110. In some embodiments, the optically transparent hard coating 120 may include an optically transparent material having a pencil hardness of 8H or greater or 9H or greater. In some embodiments, the optically transparent hard coating 120 may include an optically transparent polymeric material. In some embodiments, the optically transparent hard coating 120 may include an optically transparent polymer material having a pencil hardness of 8H or greater or 9H or greater.

Suitable materials for optically transparent hard coat layer 120 include, but are not limited to: inorganic-organic hybrid polymer materials, and aliphatic or aromatic hexafunctional urethane acrylates. As used herein, "inorganic-organic hybrid polymeric material" refers to a polymeric material that includes monomers having inorganic and organic components. The inorganic-organic hybrid polymer is obtained by a polymerization reaction between monomers having an inorganic group and an organic group. Inorganic-organic hybrid polymers are not nanocomposites (e.g., inorganic particles dispersed in an organic matrix) comprising separate inorganic and organic constituents or phases.

In some embodiments, the inorganic-organic hybrid polymer material may include a polymerized monomer including an inorganic silicon-based group, for example, a silsesquioxane polymer. The silsesquioxane polymer may be, for example: alkyl-silsesquioxanes, aryl-silsesquioxanes or compounds having the chemical structure (RSiO)_1.5) n, wherein R is an organic group such as, but not limited to, methyl or phenyl. In some embodiments, the optically clear hardcoat 120 may be a 9H durometer silsesquioxane polymer layer manufactured by Gunze, Inc.

In some embodiments, the optically clear hard coat layer 120 may be a layer comprising: 90 to 95 weight percent (wt%) aromatic hexafunctional acrylate (e.g., PU662NT (aromatic hexafunctional acrylate) manufactured by Miwon specialty chemicals) and 10 to 5 wt% photoinitiator (e.g., Darocur 1173 manufactured by Ciba specialty chemicals) having a hardness of 8H or greater. In some embodiments, the optically clear hardcoat layer 120 comprising an aliphatic or aromatic hexafunctional urethane acrylate can be formed as a free standing layer by: spin coating the layer onto a polyethylene terephthalate (PET) substrate, allowing the urethane acrylate to cure, and removing the urethane acrylate layer from the PET substrate.

Optically clear hard coat layer 120 may have a thickness 126, measured from bottom surface 122 to top surface 124 of optically clear hard coat layer 120, of 10 microns to 120 microns, including any and all subranges therebetween. For example, the thickness 126 of the optically clear hard coat layer 120 may be: 10 microns, 20 microns, 30 microns, 40 microns, 50 microns, 60 microns, 70 microns, 80 microns, 90 microns, 100 microns, 110 microns, 120 microns, or within a range having any two of these values as endpoints. For example, the thickness 126 may be: 10 to 110 microns, or 10 to 100 microns, or 10 to 90 microns, or 10 to 80 microns, or 10 to 70 microns, or 10 to 60 microns, or 10 to 50 microns, or 10 to 40 microns, or 10 to 30 microns, or 10 to 20 microns.

For example, as shown in FIG. 2, in some embodiments, an optically clear adhesive layer 130 may be disposed on the top surface 114 of the optically clear fiber glass composite layer 110, thereby bonding the optically clear hardcoat layer 120 to the optically clear fiber glass composite layer 110. Suitable optically clear adhesives for layer 130 include, but are not limited to: acrylic adhesives, for example: 3M^TM8211 or 3M^TM821X adhesive, or any liquid optically clear adhesive, e.g.

A liquid optically clear adhesive.

Optically clear adhesive layer 130 may have a thickness 136, measured from bottom surface 132 to top surface 134 of optically clear adhesive layer 130, of 5 microns to 50 microns, including any and all subranges therebetween. For example, thickness 136 of optically clear adhesive layer 130 may be: 5 microns, 10 microns, 15 microns, 20 microns, 25 microns, 30 microns, 35 microns, 40 microns, 45 microns, 50 microns, or within a range having any two of these values as endpoints. In some embodiments, the thickness 126 may be in the following range: from 5 microns to 45 microns, or from 5 microns to 40 microns, or from 5 microns to 35 microns, or from 5 microns to 30 microns, or from 5 microns to 25 microns, or from 5 microns to 20 microns, or from 5 microns to 15 microns, or from 5 microns to 10 microns.

For example, as shown in FIG. 3, the optically transparent fiberglass composite layer 110 may include a fiberglass layer 150 embedded in a matrix material 140. Suitable materials for the matrix material 140 include, but are not limited to, acrylate polymers. In some embodiments, these polymers may be crosslinked polymers. In some embodiments, the optically clear fiber glass composite layer 110 may comprise the same materials and be manufactured in the same manner as the optically clear fiber glass composite layer 630 discussed herein.

The fiberglass layer 150 may include one or more layers of glass fibers or glass fiber bundles arranged in an ordered pattern. In some embodiments, fiberglass layer 150 may comprise one or more woven fiberglass layers. As used herein, "knit layer" refers to a layer having two or more sets of fibers or fiber bundles oriented in different directions, the different sets of fibers or fiber bundles overlapping and interwoven with one another (e.g., alternating, overlapping configurations). The woven layer comprises an ordered arrangement of fibers or groups of fiber bundles on the layer. Neither the woven layer, nor any layer comprising fibers and/or bundles arranged in an ordered pattern, contains a significant amount of randomly oriented fibers or bundles of fibers. Suitable weave patterns for fiberglass layer 150 include, but are not limited to: a plain weave pattern, a twill weave pattern, a satin weave pattern, a jacquard (jacquard) pattern, and a leno weave pattern.

In some embodiments, fiberglass layer 150 may have 500 to 1500 grams per square meter (g/m)²) Including any and all subranges therebetween. For example, fiberglass layer 150 may have a minimum density of: 500g/m²、600g/m²、700g/m²、800g/m²、900g/m²、1000g/m²、1100g/m²、1200g/m²、1300g/m²、1400g/m²、1500g/m²Or within the range where any two of these values are endpoints. For example, fiberglass layer 150 may have a minimum density of: 500g/m²To 1400g/m²Or 500g/m²To 1300g/m²Or 500g/m²To 1200g/m²Or 500g/m²To 1100g/m²Or 500g/m²To 1000g/m²Or 500g/m²To 900g/m²Or 500g/m²To 800g/m²Or 500g/m²To 700g/m²Or 500g/m²To 600g/m². In some embodiments, the minimum fiber density in the fiberglass layer 150 may be about 1080g/m². The density of fibers in the fiberglass layer 150 may be selected to provide the desired mechanical properties to the optically transparent fiberglass composite layer 110. Generally, a higher fiber density of the fiberglass layer 150 results in a higher stiffness and impact and/or puncture resistance of the optically clear fiberglass composite layer 110, and vice versa.

Unless otherwise noted, the density of the fiberglass layer 150 as noted herein is measured in the absence of matrix material (e.g., prior to embedding the fiberglass layer 150 in the matrix material 140). However, in practice, the density of the fiberglass layer 150 may be measured by measuring the density of the embedded fiberglass layer 150 and excluding the density factor of the matrix material 140 after embedding the fiberglass layer 150 in the matrix material 140.

The fiberglass layer 150 may have a thickness 156, measured from the bottom surface 152 to the top surface 154 of the fiberglass layer 150, of 10 microns to 100 microns, including any and all subranges therebetween. For example, the thickness 156 may be: 10 microns, 20 microns, 30 microns, 40 microns, 50 microns, 60 microns, 70 microns, 80 microns, 90 microns, 100 microns, or within a range having any two of these values as endpoints. For example, the thickness 156 may be: 10 to 90 microns, or 10 to 80 microns, or 10 to 70 microns, or 10 to 60 microns, or 10 to 50 microns, or 10 to 40 microns, or 10 to 30 microns, or 10 to 20 microns.

In some embodiments, the fiberglass layer 150 and the matrix material 140 may be index matched materials. In such embodiments, the fiberglass layer 150 includes fibers comprising a glass material having a first refractive index and a matrix material 140 having a second refractive index, and the difference (Δ n) between the first refractive index and the second refractive index is 0.05 or less. In some embodiments, Δ n may be 0.04 or less. In some embodiments, Δ n may be 0.03 or less. In some embodiments, the glass material for fiberglass layer 150 may have a refractive index of 1.5 to 1.6, including any and all subranges therebetween. For example, the refractive index of the glass material may be 1.5, 1.51, 1.52, 1.53, 1.54, 1.55, 1.56, 1.57, 1.58, 1.59, 1.6, or within a range having any two of these values as endpoints.

Reflection occurs at material interfaces where there is a discrete change in refractive index (Δ n) between the materials. And the greater the refractive index change (Δ n), the greater the amount of reflection that can occur at the interface. Thus, index-matched fibers and matrix materials (i.e., Δ n is 0.05 or less) reduce light reflection at the interface between the fiber and the matrix material. Further, by reducing light reflection, the matched refractive index contributes to the optical transparency of the optically transparent fiber glass composite layer 110, and thus contributes to the optical transparency of the cover substrate 100. The refractive index of the matrix material 140 is the refractive index of the material in its fully consolidated state (e.g., fully cured state).

In some embodiments, the optically transparent fiber glass composite layer 110 and the optically transparent hard coating 120 may be index-matched layers. In such embodiments, the optically transparent fiber glass composite layer 110 has a first refractive index and the optically transparent hard coating 120 has a second refractive index, and the difference (Δ n) between the first refractive index and the second refractive index is 0.05 or less. Similar to the index matching between fiberglass layer 150 and matrix material 140, the index matching between

layers

110 and 120 reduces light reflection at the interface between the layers and contributes to the optical transparency of cover substrate 100.

In some embodiments, the cover substrate 100 may have a bend radius 170 (see fig. 4) of 5mm or less. In some embodiments, the cover substrate 100 may have a bend radius 170 of 4mm or less. In some embodiments, the cover substrate 100 may have a bend radius 170 of 3mm or less. When the cover substrate 100 is held at the "X" radius for at least 60 minutes at about 25 ℃ and about 50% relative humidity, the cover substrate 100 achieves the bend radius "X" if it withstands failure. For bend radius test purposes, the term "failure" means that the cover substrate delaminates, cracks, creases, separates, or otherwise becomes unsuitable for its intended use. Fig. 4 shows a bending force 172 applied to the cover substrate 100 to bend it to a bend radius 170. In some embodiments, the optically clear fiber glass composite layer 110 and/or the optically clear hard coating layer 120 may have a bend radius of 5mm or less, 4mm or less, 3mm or less, 2mm or less, or 1mm or less. The bending radii of the optically transparent fiber glass composite layer 110 may be the same or different when bent in the first transverse direction 190 and the second transverse direction 192.

Fig. 5 shows an electronic display assembly 500 comprising cover substrate 100 according to some embodiments. Electronic display assembly 500 includes an electronic display 510 that includes a bottom surface 512 and a display surface (top surface, user facing surface) 514. The electronic display 510 may be, for example: a Light Emitting Diode (LED) display or an Organic Light Emitting Diode (OLED) display. In some implementations, the electronic display 510 can be a flexible electronic display. As used herein, a flexible layer, flexible article, or flexible display is a layer, article, or display that has a bend radius of 10mm or less of its own.

The cover substrate 100, specifically the bottom surface 112 of the optically transparent fiberglass composite layer 110, is disposed above the display surface 514. In some embodiments, an optically clear adhesive layer may be disposed on the display surface 514 for bonding the optically clear fiber glass composite layer 110 to the display surface 514. In some embodiments, the thickness of the optically clear adhesive layer can be 5 microns to 50 microns, as described herein with respect to optically clear adhesive layer 130. In some embodiments, the optically transparent fiber glass composite layer 110 may be disposed on the display surface 514. In operation, cover substrate 100 is configured to protect electronic display 510 from impact and/or puncture forces. Electronic display assembly 500 may be free of a glass layer disposed between display surface 514 and optically transparent fiberglass composite layer 110. Accordingly, in some embodiments, the cover substrate 100 may be free of a glass layer present between the topmost surface and the bottommost surface of the cover substrate 100. In such embodiments, the mechanical properties provided by cover substrate 100 eliminate the need for a glass layer to provide protection for electronic display 510.

In some embodiments, the cover substrate 100 may have an impact resistance defined by the ability of the cover substrate 100 to avoid failure at pen drop heights of "Y" centimeters (cm) or greater in the pen drop test. In some embodiments, "Y" may be 7. In some embodiments, "Y" may be 8. In some embodiments, "Y" may be 9. In some embodiments, "Y" may be 10. In some embodiments, "Y" may be 11. In some embodiments, "Y" may be 12. The pen-down height and the control pen-down height were measured according to the "pen-down test" as follows.

The "pen down test" as described and referred to herein is performed as follows: a sample of the cover substrate disposed above the flexible OLED display was subjected to a load (i.e., from a pen falling at a certain height) imparted to the top surface of the cover substrate, while the opposite side of the flexible OLED display was supported by an aluminum plate (6063 aluminum alloy, polished to surface roughness with 400 mesh paper) for testing. No strip was used on the side of the sample on the aluminum plate. Using three stars

The S6 Edge OLED display was used as the flexible OLED display for the pen down test. Bonding of overlay substrate samples to samsung Using 50 micron thick strips

S6 Edge OLED display.

Drop pen tests use a catheter to guide the pen to the sample, placing the tube in contact with the top surface of the sample such that the longitudinal axis of the tube is substantially perpendicular to the top surface of the sample. The tube had an outer diameter of 2.54cm (1 inch), an inner diameter of 1.4cm (9/16 inches), and a length of 90 cm. For each test, the pen was held at the desired height using an acrylonitrile butadiene ("ABS") spacer. After each drop, the tube is repositioned relative to the sample, thereby guiding the pen to a different impact location on the sample. The pen for pen-down test is

Easy Glide Pen, Fine (Fine tip Easy-to-slide Pen) with a tungsten carbide ball-point tip of 0.7mm diameter, the weight including the cap was 5.73 g (the weight excluding the cap was 4.68 g).

For drop tests, the pen is dropped with the cap attached to the tip (i.e., the end opposite the pen tip) so that the ball point can interact with the test sample. In the drop sequence according to the pen-down test, a pen-down is performed once at an initial height of 1cm, followed by successive drops (up to 20cm) in 1cm increments, and then after 20cm, in 2cm increments until the test specimen fails. Any observable evidence of chipping, failure, or other damage to the cover substrate and/or flexible OLED display present, as well as the specific pen down height, was recorded after each drop. Using the pen down test, multiple samples can be tested according to the same drop sequence to produce a panel with statistical data improvement. For the pen drop test, after every five drops and for each new sample test, the pen was changed to a new pen. In addition, all of the strokes are performed at random locations on the sample at or near the center of the sample, and no strokes are performed at or near the edge of the sample.

For the purposes of pen down testing, "failure" of the cover substrate refers to the formation of visible mechanical defects in the cover substrate. The mechanical defect may be a crack or a plastic deformation (e.g., a surface indentation). The crack may be a surface crack or a through crack (i.e., a crack extending from one major surface through to the opposite major surface). Cracks may form on the inner or outer surface of the cover substrate. The crack may extend through all or a portion of the layers covering the substrate. The visible mechanical defect has a minimum dimension of 0.2 mm or more.

Table 1 below shows pen-down test results for 4 fiberglass composite cover substrates, one cover substrate having a glass layer and a Polyimide (PI) layer, and one cover substrate containing only a glass layer, according to the discussion herein. The 4 fiberglass composite overlay substrates had the configuration of test sample 600 as shown in fig. 6A. The glass layer and PI layer cover substrate have the configuration of test sample 602 as shown in fig. 6B. And only the cover substrate of the glass layer had the configuration of test sample 604 as shown in fig. 6C. The fiberglass composite overlay substrate data included the results from two samples of each of the 4 fiberglass composite overlay substrates. The data recorded for PI and glass layer coated substrates and glass layer only coated substrates are the average of 5 sample tests.

Each fiberglass composite overlay substrate test specimen 600 includes: an optically clear fiberglass composite layer 630 disposed over the flexible OLED display 610 by a 50 micron thick double-sided adhesive layer 620, and an optically clear hard coat layer 634 (referred to in table 1 as "HDF") bonded to the optically clear fiberglass composite layer 630 by a 25 micron thick optically clear adhesive layer 632. The optically transparent fiberglass composite layer 630 is prepared as follows. Each test specimen 600 included the same type of optically clear fiberglass composite layer 630. There was only a thickness variation of the optically transparent fiberglass composite layer 630 between samples 600. The following 4 thicknesses were tested: (a)130 microns (um), 75 microns, 120 microns, and 125 microns.

The test sample 602 includes a 50 micron thick Polyimide (PI) layer 640 bonded to a flexible OLED display 610 by a 50 micron thick double sided adhesive layer 620. And test sample 604 included a 75 micron thick ion-exchanged glass layer (75um IOX glass) 650 bonded to a flexible OLED display 610 by a 50 micron thick double-sided adhesive layer 620.

Table 1: pen down test results

As shown in table 1, when the OLED display 610 was covered with the PI layer 640, visible damage in the form of pits in the PI layer 640 occurred at 3cm, and pixel failure of the OLED display 610 (in the form of pits in the OLED) occurred at 5 cm. Also, for 75 micron thick ion-exchange strengthened glass, failure occurred at around 5cm, and pixel damage (in the form of bright spots in the OLED) occurred at 9 cm. Thus, the ion-exchanged glass provides almost twice as much puncture resistance as compared to the PI layer. However, neither the ion-exchanged glass nor the PI layer provides as good a puncture resistance as the cover substrate according to embodiments as discussed herein. When OLED display 610 was covered with a cover substrate according to embodiments discussed herein (i.e., sample 600), visible damage to the cover substrate occurred at a height of 7cm or greater, and pixel damage in OLED display 610 occurred at a height of 10cm or greater (average of about 12cm for all 4 substrates).

Fig. 7A-7C show pixel failure of OLED display 610 after testing. As shown in fig. 7A, the damage of the OLED display 610 causes a bright spot on the OLED display 610 where the pen is dropped in the pen-down test. Fig. 7B shows a damaged pixel under a microscope with a 6cm pen drop failure for an unprotected OLED display 610. Fig. 7C shows a damaged pixel under a microscope with a 15cm pen-drop height failure on an OLED display 610, which OLED display 610 is protected by an optically transparent hard coat 634 bonded to an optically transparent fiberglass composite layer 630 by a 25 micron thick optically transparent adhesive layer 632.

The optically clear fiberglass composite layer 630 for the pen drop test results reported in table 1 was prepared as follows. Preparing a resin composition by mixing until homogeneous in a glass-jacketed beaker at 60-65 ℃, the resin composition comprising: 66.5 wt% M2100 (ethoxylated (10) bisphenol A diacrylate, refractive index 1.516, Miwon specialty Chemicals, Inc.), 22 wt% PE210HA (bisphenol A epoxy acrylate, refractive index 1.562, Miwon specialty Chemicals, Inc.), 10 wt% M1142 (o-phenylphenol ethyl acrylate, refractive index 1.577, Miwon specialty Chemicals, Inc.), and 1.5 wt% Omnirad TPO-L photoinitiator (diphenyl (2,4, 6-trimethylbenzoyl) was used) Phosphine oxide, BASF (BASF) canadian limited). A portion of this resin composition was placed on a release film, a woven glass fabric (1080E-glass, 40 micron thickness, refractive index 1.560, available from Jushi Group ltd.) was placed on top of the resin-coated release film, and a second portion of the resin was placed on top of the woven glass fabric. Wetting was continued at about 60 deg.C (Celsius) for 30 minutes. The transparent composite film is covered with another layer of release film. A slight excess of resin was used to completely wet the glass fabric. A shim material is used to control thickness, and a hand-held roller is used to remove air bubbles and excess resin liquid. Then, under a nitrogen purge, a Fusion UV 300W "D" bulb was used at 50% power (UV intensity approximately 2000 mW/cm)²) To cure the film. The membrane received a dose of about 1250mJ/cm². The cured films were conditioned overnight in a controlled environment at 23 ℃ and 50% relative humidity prior to testing.

In some embodiments, the cover substrate 100 may be a 2D, 2.5D, or 3D cover substrate. As used herein, "2D cover substrate" includes cover substrates having a chamfered shaped perimeter edge on a top and/or bottom surface of the cover substrate adjacent to the perimeter edge. The chamfered shape on the top and/or bottom surface may be formed by a finishing method, for example, including mechanical grinding. The 2D cover substrate may have the same or different bevel shapes on the top and bottom surfaces of the cover substrate.

As used herein, "2.5D cover substrate" means that the cover substrate has a perimeter edge with a curved surface on its top side (user facing side). The curved surface may be formed by, for example, a mechanical polishing method. The cover surface on the top side of the 2.5D cover substrate was smoother to the touch than the chamfered surface of the 2D cover substrate. As used herein, "3D cover substrate" means that the cover substrate has a curved perimeter edge that forms a non-flat shape. The curved perimeter edge can be formed by, for example, hot forming and/or cold forming. The 3D cover substrate has a curved bottom surface and a curved top surface adjacent to a perimeter edge of the cover substrate. A 3D cover substrate refers to a cover substrate that maintains a 3D shape at room temperature (23 ℃) without being subjected to external forces (e.g., bending forces) as described herein. At room temperature, a flexible film that may deform due to its own weight is not considered a 3D cover substrate as described herein. Both the 2.5D and 3D cover substrates have a topmost exterior surface that includes a substantially flat central region and a curved perimeter region disposed about all or a portion of the substantially flat central region. The 3D cover substrate includes a bottommost outer surface that includes a substantially flat central region and a curved perimeter region disposed about all or a portion of the substantially flat central region.

Fig. 8A shows a 2D cover substrate 800 according to some embodiments. The cover substrate 800 includes a substantially planar central region 802, a chamfered perimeter region 804. The perimeter region 804 of the 2D cover substrate 800 may be finished by a mechanical grinding process to create a chamfered shape on the top surface 806 and/or the bottom surface 808 of the cover substrate 800. In some embodiments, the chamfered shapes on the top surface 806 and the bottom surface 808 of the cover substrate 800 may be the same.

Fig. 8B shows a 2.5D cover substrate 810 according to some embodiments. The 2.5D cover substrate 810 includes a substantially flat central region 812 and a curved perimeter region 814 on a top surface 816 of the cover substrate 810. The curved perimeter region 804 may be finished by a mechanical polishing process to form a curved surface on the top surface 816. Thus, the 2.5D cover substrate 810 may have a perimeter region 814 with a flat bottom surface 818 and a curved top surface 816. In some embodiments, a 2.5D cover substrate can be fabricated by mechanically polishing the perimeter region of the optically clear fiberglass composite layer and bonding an optically clear hard coating to the curved top surface.

Fig. 8C shows a 3D cover substrate 820 according to some embodiments. The 3D cover substrate 820 includes a substantially flat central region 822, a curved perimeter region 824. The 3D cover substrate 820 has a curved top surface 826 and a curved bottom surface 828 in the curved perimeter region 824. The 3D cover substrate 820 may be formed by, for example, molding an optically transparent fiber glass composite layer having a 3D shape, and bonding an optically transparent hard coating layer to the optically transparent fiber glass composite layer.

In some embodiments, for example as shown in fig. 9, the cover substrate 100 may be coated with a coating 180 having a bottom surface 182, a top surface 184, and a thickness 186. In some embodiments, the coating 180 may be bonded to the top surface 124 of the optically clear hardcoat 120. In some embodiments, the coating 180 may be disposed on the top surface 124 of the optically transparent hard coating 120. In some embodiments, multiple coatings 180 of the same or different types may be applied over the cover substrate 100.

In some embodiments, the coating 180 may be a scratch resistant coating. Exemplary materials for the scratch-resistant coating may include inorganic carbides, nitrides, oxides, oxynitrides, diamond-like materials, or combinations thereof. In some embodiments, the scratch resistant coating may include aluminum oxynitride (AlON) and silicon dioxide (SiO)₂) The multilayer structure of (3). In some embodiments, the scratch-resistant coating may comprise a metal oxide layer, a metal nitride layer, a metal carbide layer, a metal oxynitride layer, a metal boride layer, or a diamond-like carbon layer. Exemplary metals for such oxide, nitride, oxynitride, carbide, or boride layers include: boron, aluminum, silicon, titanium, vanadium, chromium, yttrium, zirconium, niobium, molybdenum, tin, hafnium, tantalum, and tungsten. In some embodiments, the coating may include an inorganic material. Non-limiting exemplary inorganic layers include alumina and zirconia layers.

In some embodiments, the scratch-resistant coating can comprise a scratch-resistant coating as described in U.S. patent No. 9,328,016 issued 5/3/2016, which is incorporated herein by reference in its entirety. In some embodiments, the scratch-resistant coating can include silicon-containing oxides, silicon-containing nitrides, aluminum-containing nitrides (e.g., AlN and Al)_xSi_yN), aluminum-containing oxynitride (e.g., AlO)_xN_yAnd Si_uAl_vO_xN_y) An aluminum-containing oxide, a silicon-containing oxynitride, or a combination thereof. In some embodiments, the scratch-resistant coating may include a transparent dielectric material, such as SiO₂、GeO₂、Al₂O₃、Nb₂O₅、TiO₂、Y₂O₃And other similar materials, and combinations thereof. In some embodiments, the scratch-resistant coating can comprise a scratch-resistant coating as described in U.S. patent No. 9,110,230 issued 8/18/2015, which is incorporated herein by reference in its entirety. In some embodiments, the scratch-resistant coating may include one or more of the following: AlN, Si₃N₄、AlO_xN_y、SiO_xN_y、Al₂O₃、Si_xC_y、Si_xO_yC_z、ZrO₂、TiO_xN_yDiamond, diamond-like carbon and Si_uAl_vO_xN_y. In some embodiments, the scratch-resistant coating can comprise a scratch-resistant coating as described in U.S. patent No. 9,359,261 issued on 7/2016 or U.S. patent No. 9,335,444 issued on 10/5/2016, both of which are incorporated herein by reference in their entirety.

In some embodiments, coating 180 may be an antireflective coating. Exemplary materials suitable for use in antireflective coatings include: SiO 2₂、Al₂O₃、GeO₂、SiO、AlO_xN_y、AlN、SiNx、SiO_xN_y、Si_uAl_vO_xN_y、Ta₂O₅、Nb₂O₅、TiO₂、ZrO₂、TiN、MgO、MgF₂、BaF₂、CaF₂、SnO₂、HfO₂、Y₂O₃、MoO₃、DyF₃、YbF₃、YF₃、CeF₃Polymers, fluoropolymers, plasma polymerized polymers, siloxane polymers, silsesquioxanes, polyimides, fluorinated polyimides, polyetherimides, polyethersulfones, polyphenylsulfones, polycarbonates, polyethylene terephthalates, polyethylene naphthalates, acrylic polymers, urethane polymers, polymethyl methacrylates, and other materials cited above as suitable for use in scratch resistant layers. The antireflective coating may comprise sublayers of different materials.

In some embodiments, the anti-reflective coating may include a layer of hexagonally-packed nanoparticles, such as, but not limited to, the hexagonally-packed nanoparticle layer described in U.S. patent No. 9,272,947 issued on 1/3/2016, which is incorporated herein by reference in its entirety. In some embodiments, the antireflective coating may comprise a nanoporous silicon-containing coating, such as, but not limited to, the nanoporous silicon-containing coating described in WO2013/106629, published 2013, 7, 18, which is incorporated herein by reference in its entirety. In some embodiments, the antireflective coating may comprise a multilayer coating, such as, but not limited to: WO2013/106638, published on day 18, 7, 2013, WO2013/082488, published on day 6, 2013, and U.S. patent No. 9,335,444, published on day 10, 5, 2016, all of which are incorporated herein by reference in their entirety.

In some embodiments, the coating may be an easy-clean coating. In some embodiments, the easy-clean coating may include a material selected from the group consisting of: fluoroalkyl silanes, perfluoropolyether alkoxysilanes, perfluoroalkyl alkoxysilanes, fluoroalkyl silane- (non-fluoroalkyl silane) copolymers, and mixtures of fluoroalkyl silanes. In some embodiments, the easy-clean coating may include one or more materials of a selected type of silane containing perfluorinated groups, such as: has the chemical formula of (R)_F)_ySi_X4-yIn which RF is a linear C6-C30 perfluoroalkyl radical, X ═ Cl, acetoxy, -OCH₃and-OCH₂CH₃And y is 2 or 3. Perfluoroalkylsilanes are commercially available from a number of commercial suppliers, including: dow Corning (Dow-Corning) (e.g., fluorocarbons 2604 and 2634), 3M companies (e.g., ECC-1000 and ECC-4000), and other fluorocarbon suppliers such as Dajin Corporation, Serke (Ceko) (Korea), Krett Corporation (Cotec-GmbH) (Duralon UltraTec materials) and Yingk (Evonik). In some embodiments, the easy-to-clean coating can comprise the easy-to-clean coating described in WO2013/082477, published 6/2013, which is incorporated herein by reference in its entirety.

In some embodiments, the coating 180 may be an antiglare layer formed on the top surface 124 of the optically transparent hard-coating 120. Suitable antiglare layers include, but are not limited to: antiglare layers made by the processes described in U.S. patent publication nos. 2010/0246016, 2011/0062849, 2011/0267697, 2011/0267698, 2015/0198752 and 2012/0281292, which are incorporated herein by reference in their entirety.

In some embodiments, the coating 180 may be an anti-fingerprint coating. Suitable anti-fingerprint coatings include, but are not limited to: oleophobic surface layers containing gas trapping features, such as described in U.S. patent application publication No. 2011/0206903 published 8/25 2011; and oleophilic coatings formed from uncured or partially cured silicone coating precursors comprising inorganic side chains (e.g., partially cured linear alkyl siloxanes) reactive with the surface of a glass or glass ceramic substrate, for example, as described in U.S. patent application publication No. 2013/0130004 published on 5/23 of 2013. The contents of U.S. patent application publication No. 2011/0206903 and U.S. patent application publication No. 2013/0130004 are incorporated herein by reference in their entirety.

In some embodiments, the coating 180 can be an antimicrobial and/or antiviral layer formed on the top surface 124 of the optically clear hardcoat 120. Suitable antimicrobial and/or antiviral layers include, but are not limited to: an antimicrobial Ag + region extending from the surface of the glass article into the depth of the glass article having a suitable concentration of Ag +1 ions on the surface of the glass article, for example, as described in U.S. patent application publication No. 2012/0034435 published on 2-9/2012 and U.S. patent application publication No. 2015/0118276 published on 4-30/2015. The contents of U.S. patent application publication No. 2012/0034435 and U.S. patent application publication No. 2015/0118276 are incorporated herein by reference in their entirety.

Fig. 10 shows a consumer product 1000 according to some embodiments. The consumer electronic product 1000 can include a housing 1002 having a front surface (user facing surface) 1004, a back surface 1006, and side surfaces 1008. The electronic components may be provided at least partially within the housing 1002. The electronic components may include a controller 1010, a memory 1012, and display components (including a display 1014), among others. In some implementations, the display 1014 can be provided at or adjacent to the front surface 1002 of the housing 1004.

For example, as shown in fig. 10, the consumer electronic product 1000 may include a cover substrate 1020. The cover substrate 1020 may function to protect the display 1014 and other components of the electronic product 1000 (e.g., the controller 1010 and the memory 1012) from damage. In some embodiments, cover substrate 1020 may be disposed over display 1014. In some embodiments, cover substrate 1020 may be bonded to display 1014. In some embodiments, the cover substrate 1020 may be a cover substrate, which is defined in whole or in part by the cover substrates discussed herein. The cover substrate 1020 may be a 2D, 2.5D, or 3D cover substrate. In some embodiments, the cover substrate 1020 may define the front surface 1004 of the housing 1002. In some embodiments, the cover substrate 1020 may define the front surface 1004 of the housing 1002 and the side surface 1008 of all or a portion of the housing 1002. In some embodiments, the consumer electronic product 1000 can include a cover substrate that defines a back surface 1006 of all or a portion of the housing 1002.

As used herein, the term "glass" is intended to include any material made at least in part from glass, including glasses and glass-ceramics. "glass-ceramic" includes materials produced by the controlled crystallization of glass. In embodiments, the glass-ceramic has a crystallinity of about 30% to about 90%. Non-limiting examples of glass-ceramic systems that may be used include: li₂O×Al₂O₃×nSiO₂(LAS system), MgO × Al₂O₃×nSiO₂(i.e., MAS system), and ZnO × Al₂O₃×nSiO₂(i.e., ZAS system).

In one or more embodiments, the amorphous substrate may include glass, which may or may not be strengthened. Examples of suitable glasses include soda lime glass, alkali aluminosilicate glass, alkali containing borosilicate glass, and alkali aluminoborosilicate glass. In some variations, the glass may be free of lithium oxide. At one or more alternative locationsIn embodiments, the substrate may comprise a crystalline substrate, such as a glass ceramic substrate (which may or may not be strengthened) or may comprise a single crystal structure, such as sapphire. In one or more embodiments, the substrate includes an amorphous substrate (e.g., glass) and a crystalline cladding (e.g., a sapphire layer, a polycrystalline aluminum oxide layer, and/or a spinel (MgAl)₂O₄) Layers).

The substrate or layer may be strengthened to form a strengthened substrate or strengthened layer. As used herein, the term "strengthened substrate" may refer to a substrate and/or layer that is chemically strengthened by, for example, ion-exchanging larger ions for smaller ions in the surface of the substrate and/or layer. However, other strengthening methods known in the art, such as thermal tempering or a mismatch in the coefficient of thermal expansion between the substrate and/or layer portions to create compressive stress and central tension regions, may also be used to form the strengthened substrate and/or layer.

When the substrate and/or layer is chemically strengthened by an ion exchange process, ions within the surface layer of the substrate and/or layer are replaced or exchanged with larger ions having the same valence or oxidation state. The ion exchange process is typically performed by immersing the substrate and/or layer in a molten salt bath containing larger ions to be exchanged with smaller ions in the substrate and/or layer. Those skilled in the art will appreciate that the parameters of the ion exchange process include, but are not limited to: bath composition and temperature, immersion time, number of immersions of the substrate and/or layer in one or more salt baths, use of multiple salt baths, other steps such as annealing and washing, etc., which are generally determined by the following factors: the composition of the substrate and/or layer and the desired Compressive Stress (CS) and the depth of layer of compressive stress (or depth of layer) of the substrate and/or layer resulting from the strengthening operation. For example, ion exchange of the alkali-containing glass substrate and/or layer may be achieved by: immersed in at least one molten salt bath containing salts such as, but not limited to, nitrates, sulfates and chlorides of larger alkali metal ions. The temperature of the molten salt bath is typically from about 380 ℃ up to about 450 ℃ and the immersion time is from about 15 minutes up to about 40 hours. However, temperatures and immersion times other than those described above may also be employed.

Additionally, non-limiting examples of ion exchange processes for immersing glass substrates in various ion exchange baths (washing and/or annealing steps performed between immersions) are described in the following documents: U.S. patent application No. 12/500,650 entitled "Glass with Compressive Surface for Consumer Applications" filed on 7/10.2009 by Douglas c.alan et al, claiming priority from U.S. provisional patent application No. 61/079,995 filed on 11.7/2008, wherein a Glass substrate is strengthened by successive ion exchange treatments performed by multiple immersions in salt baths of different concentrations; and us patent 8,312,739 entitled "Dual Stage Ion Exchange for chemical Strength learning of Glass" by Christopher M.Lee et al, published on 11/20/2012, claiming priority from U.S. provisional patent application No. 61/084,398, filed on 29/7/2008, wherein the Glass substrate is strengthened by: ion exchange is first carried out in a first bath diluted with effluent ions and then submerged in a second bath having a lower effluent ion concentration than the first bath. The contents of U.S. patent application No. 12/500,650 and U.S. patent No. 8,312,739 are incorporated herein by reference in their entirety.

While various embodiments have been described herein, they have been presented by way of example, and not limitation. It is noted that based upon the teachings and guidance set forth herein, debugging and modifications are intended to be included within the meaning and range of equivalents of the disclosed embodiments. Thus, it will be apparent to persons skilled in the relevant art that various modifications and variations can be made in the form and detail of the embodiments disclosed herein without departing from the spirit and scope of the disclosure. The elements of the embodiments presented herein are not necessarily mutually exclusive, but may be interchanged to satisfy various circumstances, as will be understood by those skilled in the art.

Embodiments of the present disclosure will be described in detail with reference to embodiments thereof as illustrated in the accompanying drawings, wherein like reference numerals are used to refer to identical or functionally similar elements. References to "one embodiment," "an embodiment," "some embodiments," "in certain embodiments," or the like, indicate that the embodiment described may include a particular feature, structure, or characteristic, but every embodiment may not necessarily include the particular feature, structure, or characteristic. Moreover, such phrases are not necessarily referring to the same embodiment. In addition, when a particular feature, structure, or characteristic is described in connection with an embodiment, it is submitted that it is within the purview of one skilled in the art to affect such feature, structure, or characteristic in connection with other ones of the embodiments whether or not explicitly described.

The disclosed examples are illustrative and not restrictive. Other suitable modifications and adjustments will generally be apparent to those skilled in the art based on various conditions and parameters, which are within the spirit and scope of this disclosure.

As used herein, the term "or" is inclusive, and more specifically, the expression "a or B" means "A, B or both a and B". Herein, exclusive "or" is specified by terms such as either "a or B" and "one of a or B.

The indefinite articles "a" and "an" when used to describe an element or component mean that there is one or at least one of the elements or components. Although these articles are often used to connote a modified noun as a singular noun, the articles "a" and "an" as used herein also include the plural unless otherwise indicated. Similarly, also as used herein, the definite article "the" also indicates that the modified noun may be singular or plural, unless otherwise indicated.

As used in the claims, "comprising" is an open transition phrase. The list of elements following the transitional phrase "comprising" is a non-exclusive example, such that elements other than those specifically listed may also be present. The phrase "consisting essentially of or" consisting essentially of, as used in the claims, limits the composition of the material to the specified material and those that do not significantly affect the basic and novel characteristics of the material. As used in the claims, "consisting of" or "consisting entirely of" limits the composition of materials to specific materials and excludes any unspecified materials.

The term "wherein" is used as an open transition phrase, is introduced to state a series of characteristics of a structure.

Unless otherwise indicated in a specific context, the numerical ranges set forth herein include upper and lower values, and the ranges are intended to include the endpoints thereof and all integers and fractions within the range. It is not intended that the scope of the claims be limited to the specific values recited, when such ranges are defined. Further, when an amount, concentration, or other value or parameter is expressed in terms of a range, one or more preferred ranges, or an upper preferred numerical range and a lower preferred numerical range, it is understood that any range by combining any pair of an upper range limit or a preferred numerical value with any lower range limit or a preferred numerical value is specifically disclosed, regardless of whether such a combination is specifically disclosed. Finally, when the term "about" is used to describe a value or an endpoint of a range, it is to be understood that the disclosure includes the particular value or endpoint referenced. Whether a value or an end-point of a range recites "about," the end-point of the value or range is intended to include two embodiments: one modified with "about" and one not.

As used herein, the term "about" means that amounts, sizes, formulations, parameters, and other variables and characteristics are not and need not be exact, but may be approximate and/or larger or smaller as desired, reflecting tolerances, conversion factors, rounding off and measurement errors and the like, and other factors known to those of skill in the art.

As used herein, the terms "substantially", "essentially" and variations thereof are intended to mean that the features described are equal or approximately the same as the numerical values or descriptions. For example, a "substantially planar" surface is intended to mean a planar or near-planar surface. Further, "substantially" is intended to mean that the two values are equal or approximately equal. In some embodiments, "substantially" may mean that the values are within about 10% of each other, such as within about 5% of each other, or within about 2% of each other.

The embodiments herein have been described above with the aid of functional building blocks illustrating the performance of specific functions and relationships thereof. Boundaries of these functional building blocks have been arbitrarily defined herein for the convenience of the description. Alternate boundaries can be defined so long as the specified functions and relationships thereof are appropriately performed.

It is to be understood that the phraseology or terminology employed herein is for the purpose of description and not of limitation. The breadth and scope of the present disclosure should not be limited by any of the above-described exemplary embodiments, but should be defined only in accordance with the following claims and their equivalents.

Claims

1. A cover substrate for an electronic display, the cover substrate comprising:

an optically transparent fiberglass composite layer comprising a fiberglass layer embedded in a matrix material and a bottom surface defining a bottommost outer surface of a cover substrate; and

an optically clear hard coat layer bonded to the top surface of the optically clear fiberglass composite layer.

2. The cover substrate of claim 1, comprising an optically clear adhesive layer disposed on and bonding an optically clear hardcoat layer to an optically clear fiber glass composite layer.

3. The cover substrate of claim 2, wherein the optically clear adhesive layer comprises a thickness of 5 microns to 50 microns.

4. The cover substrate of any one of claims 1-3, wherein the fiber glass layer comprises fibers comprising a glass material comprising a first refractive index and the matrix material comprises a second refractive index, and wherein the difference between the first refractive index and the second refractive index is 0.05 or less.

5. The cover substrate of any one of claims 1-4, wherein the fiberglass layer is a woven fiberglass layer.

6. A covering substrate according to any of claims 1 to 5, wherein the matrix material comprises a cross-linked polymeric material.

7. The cover substrate of any one of claims 1-6, wherein the optically transparent fiberglass composite layer comprises a thickness of 25 microns to 200 microns.

8. The cover substrate of any one of claims 1-7, wherein the fiberglass layer comprises a thickness of 10 microns to 100 microns.

9. The overlay substrate of any of claims 1-8, wherein the optically clear hard coating comprises a pencil hardness of 8H or greater.

10. The overlay substrate of any of claims 1-9, wherein the optically clear hardcoat layer is a polymeric layer.

11. The cover substrate of any one of claims 1-10, wherein the cover substrate comprises a bend radius of 3mm or less.

12. The cover substrate of any one of claims 1-11, wherein the topmost exterior surface of the cover substrate comprises a substantially planar central region and a curved perimeter region disposed about at least a portion of the substantially planar central region.

13. The cover substrate of any one of claims 1-12, wherein the optically transparent fiberglass composite layer comprises an elastic modulus of from 200MPa to 2500 MPa.

14. The cover substrate of any one of claims 1-13, wherein the optically transparent fiber glass composite layer comprises a first refractive index and the optically transparent hard coating comprises a second refractive index, and wherein the difference between the first refractive index and the second refractive index is 0.05 or less.

15. The cover substrate of any one of claims 1-14, wherein the cover substrate comprises an impact resistance defined by the ability of the cover substrate to avoid failure at a minimum pen drop height of 7cm in a pen-down test.

16. An electronic display assembly, comprising:

an electronic display comprising a display surface; and

a cover substrate disposed over a surface of a display, the cover substrate comprising:

an optically transparent fiberglass composite layer disposed over the display surface, and

17. The electronic display assembly of claim 16, wherein the electronic display is a flexible electronic display.

18. The electronic display of claim 16 or 17, wherein the cover substrate comprises an impact resistance defined by the ability of the cover substrate to avoid failure at a minimum pen drop height of 7cm in a pen-down test.

19. The electronic display assembly of any of claims 16-18, comprising an optically clear adhesive layer disposed on a display surface of the electronic display and bonding the optically clear fiber glass composite layer to the display surface.

20. The electronic display assembly of any of claims 16-19, wherein the electronic display assembly is free of a glass layer disposed between the display surface and the optically clear fiber glass composite layer.

21. A method of making a cover substrate for an electronic display, the method comprising:

forming an optically transparent fiberglass composite layer comprising a fiberglass layer embedded in a matrix material and a bottom surface defining a covered bottommost outer surface; and

an optically clear hard coat layer is bonded to the top surface of the optically clear fiberglass composite layer.

22. The method of claim 21, wherein bonding the optically clear hardcoat layer to the top surface of the optically clear fiber glass composite layer comprises bonding the optically clear hardcoat layer to the top surface of the optically clear fiber glass composite layer through an optically clear adhesive layer.

23. The method of claim 21 or 22, wherein bonding the optically clear hard coat layer to the top surface of the optically clear fiber glass composite layer comprises forming the optically clear hard coat layer on the top surface, and wherein forming the optically clear hard coat layer on the top surface causes the optically clear hard coat layer to bond to the top surface.

24. An article of manufacture, comprising:

a cover substrate, comprising:

an optically transparent fiberglass composite layer including a bottom surface defining a bottommost surface of a cover substrate; and

25. The article of claim 24, wherein the article is a consumer electronic product comprising:

a housing comprising a front surface, a back surface, and side surfaces;

an electronic assembly at least partially disposed within the housing, the electronic assembly including a controller, a memory, and a display, the display being located at or adjacent to the front surface of the housing; and

a cover substrate, wherein the cover substrate is disposed over the display or forms at least a portion of the housing.